CN103665387B - A kind of method preparing accurate polymer network - Google Patents
A kind of method preparing accurate polymer network Download PDFInfo
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Abstract
The invention discloses a kind of method preparing accurate polymer network, the method utilizing reversible addition-fragmentation chain transfer free radical polymerization (RAFT) and click chemistry to combine accurately controls polymer ends nitrine functional group number, thus control cross-linking set quantity prepares regular polymer cross-linked network structure.In the inventive method, polymer network is generated with containing two or more end alkynyl radical or nitrine functional group (F) click-reaction two or more official's end group nitrine accurately controlled by polymer chain terminal or alkynes functional group (E) by multistep reversible addition-fragmentation chain transfer free radical polymerization, gel the present invention has crosslinked polymer network structure cross-linking set number and density controllable precise, and is suitable for the advantage of the various polymer network structure containing different functional groups.
Description
Technical field
The invention belongs to filed of functional, relate to a kind of method preparing accurate polymer network structure based on molecular designing control polymer ends functional group number.
Background technology
Polymer mesh structure, particularly hydrogel are the materials having similar quality and performance the most with biological tissue.Hydrogel is the macromolecule network be cross-linked by hydrophilic macromolecule, and in polymer network gap, some small-molecule substances can move as in microbial film, carry out the transmission of information and material.Have high strength, accurate molecular structure and function macromolecule network owing to having similar biomembranous function, so there is the bionical organ of film function, as the aspects such as artificial blood vessel, kidney and skin have important application prospect.Therefore, the function water gel of high strength will have very important effect at the biomedical sector in future.The gel network prepared by conventional free radical polymerization process, due to crosslinking structure irregularity, stress defect is more, and therefore physical strength is not high.Except mechanical strength is lower, for the gel network in bionic films field, in biocompatibility, anti-protein adheres and stalling characteristic etc., also has higher requirement.And gelatinous material prepared by traditional method can not meet the requirement of these specific functions, because which limit the potential application of gelatinous material in Biomimetic membranes.
Click chemistry, particularly copper catalysis end, with the cycloaddition reaction (CuAAC) of nitrine/ethynylene group, have reaction conditions gentleness, transformation efficiency is high, cost is low advantage.Experiment proves, click chemistry technology can prepare the polymer network structure that molecular structure is regular, physical and mechanical properties is high.At present, by click chemistry method with polyoxyethylene glycol (PEG), poly(lactic acid), polyoxyethylene is that various polymer gel network prepared by raw material.Active free radical polymerization (LRP), as atom transfer radical polymerization (ATRP) and reversible addion-fragmentation chain transfer radical polymerization (RAFT), can synthetic molecular weight controllable precise, narrow molecular weight distribution macromole.In addition, LRP reaction conditions is gentle, suitable monomers is extensive, can prepare the high molecular polymer of different topology structure.If be effectively combined with click chemistry by living radical polymerization technique, can prepare the polymer mesh structure that molecular structure is regular, function is determined, this has important meaning for the application of exploration polymer mesh structure in the bionical device with film function.It should be noted that especially, macromolecular reactive end functional group prepared by active free radical polymerization, as monothioester and halogen group, can be converted into the nitrine for click chemistry and ethynylene group easily, this is that click chemistry combines with living radical polymerization technique and prepares regular polymer network structure and provide possibility.But at present by the initiation of living-radical polymers point being carried out the end group conversion of single functionality, a namely active initiation dot generation nitrine or ethynylene group, this can not meet the requirement of preparation gel network polyfunctionality, strongly limit binding activities radical polymerization and click chemistry is preparing the application in functional polymer gel network.
Therefore need to study a kind of method that accurately can control the number of polymer ends nitrine/alkynes, thus the cross-linking set number controlling polymer network structure prepares the polymer gel structure of compound with regular structure.
Summary of the invention
Technical problem: the invention provides a kind of realize accurately controlling cross-linked network structure cross-linking set number and density, accurately can control the method that polymer ends functional group number object prepares accurate polymer network.
Technical scheme: the method preparing accurate polymer network of the present invention, comprises following reactions steps:
A) adopting the double bond monomer (A) containing function functional group, take azo-bis-isobutyl cyanide as initiator, difunctionality three thioesters
for chain-transfer agent, three's mol ratio is 50:0.05:1 ~ 1000:0.2:1, and the obtained end of reaction is with the linear polymer (B) of trithio ester functional group;
B) with N-maleimide
for function monomer, Diisopropyl azodicarboxylate is initiator, and linear polymer (B) prepared by step a) is Macromolecular chain transfer agent, and three's mol ratio is 2:0.01:1 ~ 100:1:1, and obtained polymer ends is containing the linear polymer (C) of functional group R ';
C) take beta-pinene as monomer, Diisopropyl azodicarboxylate is initiator, the polymkeric substance (C) of step b) synthesis is Macromolecular chain transfer agent, three mol ratio 2:0.01:1 ~ 100:1:1, and obtained polymer ends contains the linear polymer (D) of beta-pinene functional group and R ' functional group;
D) line polymer (D) prepared with step c) is for Macromolecular chain transfer agent, according to step b) and method flow c), again carry out reversible addition-fragmentation chain transfer free radical polymerization reaction, so repeated multiple times, during each reversible addition-fragmentation chain transfer free radical polymerization reaction, the line polymer (D) generated in all reacting with reversible addition-fragmentation chain transfer free radical polymerization last time is for Macromolecular chain transfer agent, thus final obtained end group contains the polymkeric substance (E) of multiple R ' functional group;
E) click chemistry: the polymkeric substance (E) that end group step d) prepared contains multiple R ' functional group occurs to click chemical reaction with polymkeric substance (F), obtain regular cross-linked network structure, polymkeric substance F) be the high polymer containing two or more nitrine, alkynyl or sulfydryl, its molecular weight is 500 ~ 20000.
In the inventive method, monomer (A) is NIPA, pentafluorostyrene, Sodium styrene sulfonate, Styrene and its derivatives, tert-butyl acrylate, methyl methacrylate, methacrylic acid dihydroxy ethyl ester, 2-(dimethylamine) ethylmethyl acrylate, any one in vinyl cyanide.
In the inventive method, difunctionality three thioesters in step a)
r functional group is wherein ethylene glycol isopropyl acid esters, ethylene glycol isopropyl acid ester derivative or to benzene diisopropyl acyl, Z substituting group is phenyl ring or alkyl, and ethylene glycol isopropyl acid ester derivative is polyoxyethylene glycol isobutyrate, propylene glycol isobutyl acid esters or butyleneglycol isobutyrate.
In the inventive method, the N-maleimide in step b)
on substituent R ' be halohydrocarbon or alkynyl.
In the inventive method, the molecular weight of the linear polymer (B) prepared in step a) is 1000 ~ 60000, and molecular weight distribution index is 1.09 ~ 1.10.
In the inventive method, the number that polymkeric substance (E) end contains R ' functional group is the number of times by controlling reversible addition-fragmentation chain transfer free radical polymerization reaction, i.e. repeating step c) reach to the number of times of step d).
In the inventive method, monomer (A) prepares polymer chain (B) by reversible addition-fragmentation chain transfer free radical polymerization, and employing azo-bis-isobutyl cyanide is initiator, temperature of reaction 40 ~ 70 DEG C, reaction is to the scheduled time, and molecular weight is at 2000-6000, and distribution coefficient is between 1.09-1.10.
Above-mentioned chain-transfer agent is that trithiocarbonate functional group is contained at two ends
chain-transfer agent, R functional group can be that ethylene glycol isopropyl acid esters and derivative thereof are as polyoxyethylene glycol isobutyrate, propylene glycol isobutyl acid esters, butyleneglycol isobutyrate etc., with to benzene diisopropyl acyl etc., Z substituting group is phenyl ring or alkyl, and wherein preferably R group is ethylene glycol isopropyl acid esters, and Z group is dodecyl.
Adopt N-maleimide
for monomer, azo-bis-isobutyl cyanide, polymer chain (B) for Macromolecular chain transfer agent in organic solvent, temperature of reaction 40 ~ 70 DEG C, in 12 ~ 24 hours reaction times, obtained two ends are respectively containing the linear polymer of a 3-bromopropyl maleimide, and molecular weight distribution index is between 1.09-1.10.
Employing beta-pinene is monomer, azo-bis-isobutyl cyanide, by above-mentioned two ends respectively containing the linear polymer of a 3-bromopropyl maleimide be Macromolecular chain transfer agent in organic solvent, temperature of reaction 40 ~ 70 DEG C, 12 ~ 24 hours reaction times, the linear polymer of obtained two ends respectively containing firpene, molecular weight distribution index is between 1.09-1.10.
Repeatedly repeat above two steps, the linear polymer (E) of obtained end at least respectively containing two or more N-maleimide functionality.
N-maleimide
substituent R ' be halohydrocarbon, alkynyl etc.
The optional toluene of solvent, methyl-phenoxide, 1,2-ethylene dichloride, N, N '-dimethyl methane amide, tetrahydrofuran (THF).
If by the linear polymer of end containing N-bromopropyl maleimide, under toluene solution 60 DEG C of conditions of excessive Diisopropyl azodicarboxylate, reaction 12 ~ 24 hours, removes terminal thioester.The polymkeric substance of gained and sodiumazide mol ratio 1:10, at N, react in N '-dimethyl formamide soln, temperature of reaction 30 ~ 60 DEG C, and react 24 ~ 48 hours, obtained end contains two or more azido polymers.
Azido-, alkynyl and a sulfydryl are at least respectively contained in polymkeric substance (F) two ends, as the polyoxyethylene glycol of two ends respectively containing an alkynyl.Macrogol ester containing alkynyl is obtained by polyoxyethylene glycol and the esterification of 3-propargyl bromide.
Above-mentioned monomer (E) is clicked with (F) under catalyst system effect, forms regular polymer network.Wherein E and F mol ratio prioritizing selection azido-: alkynyl mol ratio is 1:1.
Catalyzer is transition-metal catalyst, can adopt Fe-series catalyst, rhodium series catalysts as RhCl(PPh3) etc., lithium molybdenum (V) complex systems, rhenium system (V) catalyzer or Cu-series catalyst, as cuprous bromide or cuprous chloride.Preferred cuprous bromide.
Part is nitrogenous polydentate ligand system, as 2,2 '-dipyridyl and derivative thereof or N, N, N ', N ' ', N ' '-five methyl diethylentriamine, Tetramethyl Ethylene Diamine 1, Isosorbide-5-Nitrae, 7,10,10 – hexamethyl Triethylenetetramine (TETA)s (HMTETA) and three (N, N-dimethyl aminoethyl) amine, N-n-hexyl-2 pyridinyl carboxamide.Preferred N, N, N ', N ' ', N ' '-five methyl diethylentriamine.
Solvent can be selected from toluene, ethyl acetate, methyl-phenoxide, 1,2-ethylene dichloride, N, N '-dimethyl methane amide, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane.Preferred N, N '-dimethyl methane amide, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane.
Excessive metalcatalyzing agent in the crosslinked polymer network structure obtained by aforesaid method can be gone out with EDTA solution.Obtain colorless transparent gel.
Regularity polymer network structure prepared by the inventive method, its regularity structure is that the basis based on molecular designing is formed through reversible addition-fragmentation chain transfer free radical polymerization (RAFT).
Beneficial effect: the present invention compared with prior art, has the following advantages:
1. the present invention provides a kind of feasible method for preparing the macromolecule network with accurate molecular structure and controllable function in conjunction with click chemistry (CuAAC) and active free radical polymerization (RAFT);
2. the present invention first ingenious maleimide and the firpene of utilizing autohemagglutination and RAFT polymerization can not can repeat the characteristic that multistep causes, accurately functional group is controllably introduced macromole desired location.This method being based upon accurately regulation and control macromole functional group number and molecular structure in the accurate synthetic technology of macromole is that traditional technology is difficult to realize.
3. method of the present invention can simply and easily at the accurate controlling functions group of macromole specified location, thus can prepare the polymer gel network that function and molecular topology accurately control, and this is that the mode of simple functional group conversion is in the past inaccessiable.
4. the polymer gel network prepared of the present invention, fully combines the feature of the reaction of RAFT active free radical polymerization and click chemistry.Gel network prepared by this method has that molecular structure is regular, molecular topology is various and the feature of function controllable precise, and this is that existing method has no idea to realize.
5. the method preparing compound with regular structure high-performance gel network of the present invention's development, for gelatinous material provides possibility in the application in bionic membrane material field.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.Scope of the present invention is not limited with embodiment, but is limited by the scope of claim.
The method preparing regular polymer network of the present invention, comprises following reactions steps:
Embodiment 1: the preparation of polystyrene/polyoxyethylene glycol amphipathic gel
A) accurately take dodecyl trithio isopropylformic acid 3g, 1-ethyl-(3-dimethylamino-propyl) carbodiimide hydrochloride 3.1642g, is dissolved in 80ml methylene dichloride, stirs 10 minutes in nitrogen atmosphere.Add ethylene glycol 0.255g again and react 24 hours.After reaction terminates, reaction solution uses 1mol/L sodium bicarbonate and distilled water wash three times respectively, organic phase anhydrous magnesium sulfate drying, methylene dichloride is removed with Rotary Evaporators after being filtered by anhydrous magnesium sulfate, crude product chromatography column is separated, eluent is normal hexane: methylene dichloride=1:1, obtains two dodecyl trithiocarbonate 1.3g.
The RAFT polymerization of polystyrene: with vinylbenzene 0.833ml for monomer, azo-bis-isobutyl cyanide (0.00119g) is initiator, two dodecyl trithiocarbonate (0.09558g) is chain-transfer agent, mol ratio is 50:0.05:1, temperature of reaction is 60 DEG C, 9 hours reaction times, add the tetrahydrofuran (THF) dissolved product that monoploid is long-pending, the tetrahydrofuran (THF) being dissolved with product is added drop-wise in the methyl alcohol of 20 times of volumes, product is precipitated, filter, then vacuum-drying to constant weight obtains the polystyrene of end with trithio ester functional group;
B) accurately take maleic anhydride 6.72g and 3-propantheline bromide hydrobromide 15g is dissolved in 200ml methylene dichloride, slowly drip 10.5ml triethylamine at 0 DEG C, be slowly warming up to room temperature, stir 2.5 hours.Remove methylene dichloride with Rotary Evaporators, solid is dissolved in methylene dichloride and drips 1.25ml Hydrogen bromide, stir half an hour.Wash with the hydrobromic acid solution of 1mol/L, extract the organic over anhydrous dried over mgso obtained and spend the night.Anhydrous magnesium sulfate is filtered, adopts Rotary Evaporators to remove methylene dichloride and obtain white solid 10g.Accurately take above-mentioned white solid 6.21g, anhydrous sodium acetate 1.1g, be dissolved in 65ml diacetyl oxide, condensing reflux 24 hours under 110 DEG C of conditions.Reaction solution is poured in the sodium hydroxide solution of 400ml1mol/L and be adjusted to pH=7.0, with dichloromethane extraction, obtain organic over anhydrous dried over mgso 8 hours.Filtered by anhydrous magnesium sulfate, remove methylene dichloride with Rotary Evaporators, crude product chromatography column is separated, and eluent is methylene dichloride, obtains the finished product 1.2g.
Polystyrene/N-3-bromopropyl maleimide amine copolymer: with N-3-bromopropyl maleimide 0.0248g for monomer, Diisopropyl azodicarboxylate (0.00009g) is initiator, above-mentioned steps 1) end that synthesizes is Macromolecular chain transfer agent with the polystyrene 0.35g of trithio ester functional group, mol ratio is 2:0.01:1, be dissolved in toluene solvant 1ml, temperature of reaction is 60 DEG C, 24 hours reaction times, add appropriate tetrahydrofuran (THF) dissolved product, the tetrahydrofuran (THF) being dissolved with product is added drop-wise in the methyl alcohol of 20 times of volumes, product is precipitated, filter, then vacuum-drying to constant weight obtains the polystyrene/N-3-bromopropyl maleimide copolymer of end with trithio ester functional group.
C) polystyrene end/N-3-bromopropyl maleimide/beta-pinene copolymerization: with beta-pinene 0.019ml for monomer, Diisopropyl azodicarboxylate (0.00005g) is initiator, polystyrene/N-3-bromopropyl the maleimide copolymer (0.2g) of above-mentioned synthesis is Macromolecular chain transfer agent, mol ratio is 2:0.01:1, be dissolved in 1, in 2-ethylene dichloride 2ml solvent, temperature of reaction is 60 DEG C, 24 hours reaction times, add appropriate tetrahydrofuran (THF) dissolved product, the tetrahydrofuran (THF) being dissolved with product is added drop-wise in the methyl alcohol of 20 times of volumes, product is precipitated, filter, then vacuum-drying to constant weight obtains the polystyrene/N-3-bromopropyl maleimide/beta-pinene multipolymer of end with trithio ester functional group.
D) with the polymer macromolecule prepared for Macromolecular chain transfer agent, alternately perform step (b) and (c), by the control of polymerization procedure number of times, prepare the polymkeric substance that end group has the bromo functional groups end group of exact number.
E) preparation of end alkynyl radical PEG: accurately take PEG(M under room temperature condition
n=2000) and sodium hydride 0.432g be dissolved in 50ml anhydrous tetrahydro furan solvent, in nitrogen atmosphere stir 3 hours, accurately take propine bromine (2ml) and be dissolved in 20ml anhydrous tetrahydro furan.Under 0 DEG C of condition, utilize constant voltage ground liquid funnel to be slowly added dropwise in polyoxyethylene glycol tetrahydrofuran solution about (20 minutes) under propine bromine tetrahydrofuran solution.Slowly be warming up to room temperature, react 12 hours under magnetic agitation.Obtain product neutral alumina and diatomite removal sodium hydride, remove tetrahydrofuran (THF) with rotary evaporation, resultant product precipitates in ether, obtains white powder 4.5g.
Click chemistry prepares Vinyl ether structure: brominated hydrophobic polymer step d) prepared is at N, and the N '-dimethyl methane amide sodiumazide of ten times replaces the obtained hydrophobic polymer containing nitrine; Hydrophobic polymer above-mentioned end being contained four and six nitrine functional groups respectively with end alkynyl radical macrogol ester (M
n=2000) 0.16g/0.24g is dissolved in 1ml methylene dichloride and makes polymer dissolution, respectively be added on 0.002g/0.003gCuBr catalysis and 10 μ l/15 μ lN wherein, N, N ', N ' ', N ' '-five methyl diethylentriamine (PMDETA), sonic oscillation 2 minutes, react 12 hours under 50 DEG C of conditions, obtained gel.
Embodiment 2: the preparation of polystyrene/polyoxyethylene glycol amphipathic gel
Basic procedure and operation are with embodiment 1, and difference is:
In step a), styrene monomer is 16.6ml, and initiator azo-bis-isobutyl cyanide is 0.476g;
In step b), N-3-bromopropyl maleimide gets 1.42g, and initiator azo-bis-isobutyl cyanide is 0.09g;
In step c), beta-pinene gets 4.75ml, and initiator Diisopropyl azodicarboxylate gets 0.05g.
All the other and embodiment 1 are completely the same.
Embodiment 3: the preparation of polystyrene/polyoxyethylene glycol amphipathic gel
Basic procedure and operation are with embodiment 1, and difference is:
In step a), styrene monomer is 5ml, and initiator azo-bis-isobutyl cyanide is 0.003g;
In step b), N-3-bromopropyl maleimide 0.124g, initiator azo-bis-isobutyl cyanide is 0.0009g;
In step c), beta-pinene 0.095ml, initiator Diisopropyl azodicarboxylate (0.0005g).
All the other and embodiment 1 are completely the same.
Embodiment 4: polyacrylic acid pH responds the preparation of gel
A) accurately take dodecyl trithio isopropylformic acid 3g, 1-ethyl-(3-dimethylamino-propyl) carbodiimide hydrochloride 3.1642g, is dissolved in 80ml methylene dichloride, stirs 10 minutes in nitrogen atmosphere.Add ethylene glycol 0.255g again and react 24 hours.After reaction terminates, reaction solution uses 1mol/L sodium bicarbonate and distilled water wash three times respectively, organic phase anhydrous magnesium sulfate drying, methylene dichloride is removed with Rotary Evaporators after being filtered by anhydrous magnesium sulfate, crude product chromatography column is separated, eluent is normal hexane: methylene dichloride=1:1, obtains final product 1.3g.
The RAFT polymerization of the polyacrylic acid tert-butyl ester: take tert-butyl acrylate as monomer 5ml, azo-bis-isobutyl cyanide (0.001885g) is initiator, two dodecyl trithiocarbonate (0.0857g) is chain-transfer agent, mol ratio is 300:0.2:1, temperature of reaction is 60 DEG C, 9 hours reaction times, add the tetrahydrofuran (THF) dissolved product that monoploid is long-pending, the tetrahydrofuran (THF) being dissolved with product is added drop-wise in methanol/water (volume ratio 1::1) solution, product is precipitated, filter, then vacuum-drying to constant weight obtains the polyacrylic acid tert-butyl ester of end with trithio ester functional group;
B) be dissolved in 50mL acetone by maleic anhydride 10.3g, be placed in the round-bottomed flask of 250mL, 3-propargylamine 5.8g is dissolved in 25mL acetone, is then dropwise added drop-wise to round-bottomed flask with dropping funnel, ice bath.After reaction 1h, underpressure distillation removing acetone, then recrystallization in methyl alcohol, suction filtration, dry, obtain intermediate N butyl maleinamic acid.
N-proyl maleinamic acid 17.1g and 7g anhydrous sodium acetate is added, 50mL diacetyl oxide in the round-bottomed flask of 100mL.In 80oC oil bath, react 1h, pour in 150mL frozen water and stir, slowly add the pH of anhydrous Na OH regulator solution to neutral.Then 30mL dichloromethane extraction is used three times, the anhydrous anhydrous magnesium sulfate drying mistake of organic phase.Filtered by anhydrous magnesium sulfate, remove methylene dichloride with Rotary Evaporators, crude product chromatography column is separated, and eluent is methylene dichloride, obtains the finished product 1.2g.
The polyacrylic acid tert-butyl ester/N-propargyl maleimide amine copolymer: with N-propargyl maleimide 0.071g for monomer, Diisopropyl azodicarboxylate (0.0009g) is initiator, the polyacrylic acid tert-butyl ester 0.35g that above-mentioned steps (1) is synthesized is Macromolecular chain transfer agent, mol ratio is 10:0.1:1, be dissolved in toluene solvant 1ml, temperature of reaction is 60 DEG C, 24 hours reaction times, add appropriate tetrahydrofuran (THF) dissolved product, the tetrahydrofuran (THF) being dissolved with product is added drop-wise in methanol/water (volume ratio 1::1) solution, product is precipitated, filter, then vacuum-drying to constant weight obtains the polystyrene/N-propargyl maleimide copolymer of end with trithio ester functional group,
C) the polyacrylic acid tert-butyl ester/N-3-propargyl maleimide/beta-pinene copolymerization: with beta-pinene 0.095ml for monomer, Diisopropyl azodicarboxylate (0.0005g) is initiator, polystyrene/N-3-propargyl the maleimide copolymer (0.2g) of above-mentioned synthesis is Macromolecular chain transfer agent, mol ratio is 10:0.1:1, be dissolved in 1, in 2-ethylene dichloride 2ml solvent, temperature of reaction is 60 DEG C, 24 hours reaction times, add appropriate tetrahydrofuran (THF) dissolved product, the tetrahydrofuran (THF) being dissolved with product is added drop-wise to methanol/water (volume ratio 1:1), product is precipitated, filter, then vacuum-drying to constant weight obtains the polystyrene/N-3-bromopropyl maleimide/beta-pinene multipolymer of end with trithio ester functional group,
D) repeating step b) and c), prepare end and contain respectively containing the polymkeric substance that four and six alkynyls can roll into a ball.
E) in 100ml flask, accurately take the PEGM of double head belt epoxy-functional
n=20005g, sodiumazide 3.25g, ammonium chloride 0.27g is dissolved in 40mlN, the mixed solvent of N '-dimethyl formamide/water (volume ratio 1:1), stirs 24 hours under 50 DEG C of conditions.Reaction terminates rear dichloromethane extraction, and with anhydrous magnesium sulfate drying 12 hours, filtration anhydrous magnesium sulfate, filtrate removed methylene dichloride with Rotary Evaporators, vacuum-drying.
Click chemistry prepares pH responsive polymer network structure: prepared by step d) respectively containing four, each 0.1g of tert-butyl acrylate polymkeric substance of six alkynyls respectively with end azido-macrogol ester (M
n=2000) 0.16g/0.24g is dissolved in 1ml methylene dichloride and makes polymer dissolution, brother is added on 0.002g/0.003gCuBr catalysis and 10 μ l/15 μ lN wherein, N, N ', N ' ', N ' '-five methyl diethylentriamine (PMDETA), sonic oscillation 2 minutes, react 12 hours under 50 DEG C of conditions, obtained gel.It is fully swelling at 50ml anhydrous methylene chloride that 100ml flask put into by obtained gel, drips 4ml trifluoroacetic acid hydrolysis and stir six hours, clean with methylene dichloride.Obtained poly propenoic acid ethylene glycol pH responsive gel.
Embodiment 5: the preparation of poly N-isopropyl acrylamide/polyoxyethylene glycol thermo-responsive hydro gel
Basic procedure and operation are with embodiment 4, and difference is:
In step a), take NIPA as monomer, get 0.390g, dissolve in methyl alcohol, sedimentation and filtration in ether, final obtained end strips three thioesters functional group poly N-isopropyl acrylamide;
In step b), polymkeric substance dissolves in methyl alcohol, sedimentation and filtration in ether, and final obtained end is with the poly N-isopropyl acrylamide/N-propargyl maleimide copolymer of trithio ester functional group;
In step c), polymkeric substance dissolves in methyl alcohol, sedimentation and filtration in ether, and final obtained end is with the poly N-isopropyl acrylamide/N-propargyl maleimide/beta-pinene multipolymer of trithio ester functional group;
In step e), gel does not need to use trifluoroacetic acid hydrolysis.
All the other and embodiment 4 are completely the same.
Embodiment 6: the preparation of poly-pentafluorostyrene/polyoxyethylene glycol amphipathic gel
Basic procedure and operation are with embodiment 1, and difference is:
In step a), take pentafluorostyrene as monomer, get 0.421g, dissolve in tetrahydrofuran (THF), sedimentation and filtration in methyl alcohol, final end processed is with the poly-pentafluorostyrene of trithio ester functional group;
In step b), polymkeric substance dissolves in tetrahydrofuran (THF), sedimentation and filtration in methyl alcohol, and final obtained end is with the poly-pentafluorostyrene/N-3-bromopropyl maleimide copolymer of trithio ester functional group;
In step c), polymkeric substance dissolves in tetrahydrofuran (THF), sedimentation and filtration in methyl alcohol, and final obtained end is with the poly-pentafluorostyrene/N-3-bromopropyl maleimide/beta-pinene multipolymer of trithio ester functional group;
All the other and embodiment 1 are completely the same.
Embodiment 7: the preparation of sodium polystyrene sulfonate/polyoxyethylene glycol ionic gel
Basic procedure and operation are with embodiment 4, and difference is:
In step a), Sodium styrene sulfonate is 0.709g, dissolves in methyl alcohol, sedimentation and filtration in ether, final obtained end strips three thioesters functional group sodium polystyrene sulfonate;
In step b), polymkeric substance dissolves in methyl alcohol, sedimentation and filtration in ether, final obtained end strips three thioesters functional group sodium polystyrene sulfonate/N-propargyl maleimide copolymer;
In step c), polymkeric substance dissolves in methyl alcohol, sedimentation and filtration in ether, final obtained end strips three thioesters functional group polystyrolsulfon acid/N-propargyl maleimide sodium/beta-pinene multipolymer;
In step e), gel does not need to use trifluoroacetic acid hydrolysis.
All the other and embodiment 4 are completely the same.
Embodiment 8: the preparation of polymethylmethacrylate/polyoxyethylene glycol thermo-responsive hydro gel
Basic procedure and operation are with embodiment 4, and difference is:
In step a), methyl methacrylate 0.344g, dissolves in tetrahydrofuran (THF), and methanol extraction filters, final obtained end strips three thioesters functional group polymethylmethacrylate;
In step b), polymkeric substance dissolves in tetrahydrofuran (THF), sedimentation and filtration in methyl alcohol, final obtained end strips three thioesters functional group polymethylmethacrylate/N-propargyl maleimide copolymer;
In step c), polymkeric substance dissolves in tetrahydrofuran (THF), sedimentation and filtration in methyl alcohol, final obtained end strips three thioesters functional group polymethylmethacrylate/N-propargyl maleimide/beta-pinene multipolymer
In step e), gel does not need to use trifluoroacetic acid hydrolysis.
All the other and embodiment 4 are completely the same.
Embodiment 9: the preparation of polymethyl acrylic acid dihydroxy ethyl ester/polyoxyethylene glycol thermo-responsive hydro gel
Basic procedure and operation are with embodiment 1, and difference is:
In step a), with methacrylic acid dihydroxy ethyl ester for monomer, get 0.448g, dissolve in tetrahydrofuran (THF), sedimentation and filtration in methyl alcohol, final end processed is with the polymethyl acrylic acid dihydroxy ethyl ester of trithio ester functional group;
In step b), polymkeric substance dissolves in tetrahydrofuran (THF), sedimentation and filtration in methyl alcohol, and final obtained end is with the polymethyl acrylic acid dihydroxy ethyl ester/N-3-bromopropyl maleimide copolymer of trithio ester functional group;
In step c), polymkeric substance dissolves in tetrahydrofuran (THF), sedimentation and filtration in methyl alcohol, and final obtained end is with the polymethyl acrylic acid dihydroxy ethyl ester/N-3-bromopropyl maleimide/beta-pinene multipolymer of trithio ester functional group;
All the other and embodiment 1 are completely the same.
Embodiment 10: poly-2-(dimethylamine) preparation of ethylmethyl acrylate/polyoxyethylene glycol thermo-responsive hydro gel
Basic procedure and operation are with embodiment 4, and difference is:
In step a), with 2-(dimethylamine) ethylmethyl acrylate is monomer, gets 0.689g, dissolves in tetrahydrofuran (THF), sedimentation and filtration in methyl alcohol, final end processed is with the poly-2-(dimethylamine of trithio ester functional group) ethylmethyl acrylate;
In step b), polymkeric substance dissolves in tetrahydrofuran (THF), sedimentation and filtration in methyl alcohol, and final obtained end is with the poly-2-(dimethylamine of trithio ester functional group) ethylmethyl acrylate/N-propargyl maleimide copolymer;
In step c), polymkeric substance dissolves in tetrahydrofuran (THF), sedimentation and filtration in methyl alcohol, and final obtained end is with the poly-2-(dimethylamine of trithio ester functional group) ethylmethyl acrylate/N-propargyl maleimide/beta-pinene multipolymer;
In step e), gel does not need to use trifluoroacetic acid hydrolysis.
All the other and embodiment 4 are completely the same.
Embodiment 11: the preparation of polyacrylonitrile/polyoxyethylene glycol thermo-responsive hydro gel
Basic procedure and operation are with embodiment 4, and difference is:
In step a), take vinyl cyanide as monomer, get 0.526g, dissolve in tetrahydrofuran (THF), sedimentation and filtration in methyl alcohol, final end processed is with the polyacrylonitrile of trithio ester functional group;
In step b), polymkeric substance dissolves in tetrahydrofuran (THF), sedimentation and filtration in methyl alcohol, and final obtained end is with the polyacrylonitrile/N-propargyl maleimide copolymer of trithio ester functional group;
In step c), polymkeric substance dissolves in tetrahydrofuran (THF), sedimentation and filtration in methyl alcohol, and final obtained end is with the polyacrylonitrile/N-propargyl maleimide/beta-pinene multipolymer of trithio ester functional group;
In step e), gel does not need to use trifluoroacetic acid hydrolysis.
All the other and embodiment 4 are completely the same.
Claims (5)
1. prepare a method for accurate polymer network, it is characterized in that, the method comprises following reactions steps:
A) adopting the double bond monomer (A) containing function functional group, take azo-bis-isobutyl cyanide as initiator, difunctionality three thioesters
for chain-transfer agent, three's mol ratio is 50:0.05:1 ~ 1000:0.2:1, the obtained end of reaction is with the linear polymer (B) of trithio ester functional group, wherein R functional group is ethylene glycol isopropyl acid esters, ethylene glycol isopropyl acid ester derivative or to benzene diisopropyl acyl, Z substituting group is phenyl ring or alkyl;
B) with N-maleimide
for function monomer, Diisopropyl azodicarboxylate is initiator, the linear polymer (B) that described step a) is prepared is Macromolecular chain transfer agent, three's mol ratio is 2:0.01:1 ~ 100:1:1, obtained polymer ends contains the linear polymer (C) of functional group R ', wherein N-maleimide
on substituent R ' be halohydrocarbon or alkynyl;
C) take beta-pinene as monomer, Diisopropyl azodicarboxylate is initiator, described step b) polymkeric substance (C) that synthesizes is Macromolecular chain transfer agent, three mol ratio 2:0.01:1 ~ 100:1:1, obtained polymer ends contains the linear polymer (D) of beta-pinene functional group and R ' functional group;
D) with described step c) line polymer (D) prepared is Macromolecular chain transfer agent, according to step b) and method flow c), again carry out reversible addition-fragmentation chain transfer free radical polymerization reaction, so repeated multiple times, during each reversible addition-fragmentation chain transfer free radical polymerization reaction, the line polymer (D) generated in all reacting with reversible addition-fragmentation chain transfer free radical polymerization last time is for Macromolecular chain transfer agent, thus final obtained end group contains the polymkeric substance (E) of multiple R ' functional group;
E) click chemistry: by described steps d) end group that the prepares polymkeric substance (E) that contains multiple R ' functional group occurs to click chemical reaction with polymkeric substance (F), obtain regular cross-linked network structure, described polymkeric substance F) be the high polymer containing two or more nitrine, alkynyl or sulfydryl, its molecular weight is 500 ~ 20000.
2. the method preparing accurate polymer network according to claim 1, it is characterized in that, described step a) in monomer (A) be NIPA, any one in pentafluorostyrene, Sodium styrene sulfonate, Styrene and its derivatives, tert-butyl acrylate, methyl methacrylate, methacrylic acid dihydroxy ethyl ester, 2-(dimethylamine) ethylmethyl acrylate, vinyl cyanide.
3. the method preparing accurate polymer network according to claim 1, is characterized in that, described step a) in difunctionality three thioesters
in R functional group wherein, described ethylene glycol isopropyl acid ester derivative is polyoxyethylene glycol isobutyrate, propylene glycol isobutyl acid esters or butyleneglycol isobutyrate.
4. the method preparing accurate polymer network according to claim 1,2 or 3, it is characterized in that, described step a) in the molecular weight of linear polymer (B) for preparing be 1000 ~ 60000, molecular weight distribution index is 1.09 ~ 1.10.
5. the method preparing accurate polymer network according to claim 1,2 or 3, it is characterized in that, number that described polymkeric substance (E) end contains R ' functional group is the number of times by the reaction of control reversible addition-fragmentation chain transfer free radical polymerization, i.e. repeating step c) to steps d) number of times reach.
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| CN103897201B (en) * | 2014-04-09 | 2016-04-13 | 东南大学 | A kind of method preparing QAS polymer network |
| CN105344257B (en) * | 2015-11-19 | 2017-12-19 | 中国科学院山西煤炭化学研究所 | Polyacrylonitrile ultrafiltration film and preparation method containing 1,2,3,4 tetrazole |
| CN105542189B (en) * | 2016-02-04 | 2018-04-10 | 湖北大学 | A kind of monomer, a kind of two-dimensional material and its production and use |
| CN106366217B (en) * | 2016-08-29 | 2018-06-08 | 中山大学 | A kind of polymers function microballoon for cutting off stabilizer and preparation method thereof |
| CN106279469B (en) * | 2016-08-29 | 2018-06-08 | 中山大学 | A kind of quick method for preparing clean polymer microballoon |
| CN106496568B (en) * | 2016-10-17 | 2019-06-21 | 东华大学 | Amphipathic copolymer networks of a kind of cleaning anti-pollution type and preparation method thereof |
| CN106700086B (en) * | 2016-11-22 | 2019-06-11 | 鲁东大学 | A kind of preparation method for the polymer brush can be used for chemical-biological sensing |
| CN108864385B (en) * | 2018-05-29 | 2020-08-04 | 上海交通大学 | Preparation method of polymer brush containing precise modification sites |
| CN108948363A (en) * | 2018-06-05 | 2018-12-07 | 常州大学 | A method of preparing the multiple response hydrogel of ordered structure |
| CN114634639B (en) * | 2022-02-28 | 2024-01-09 | 南开大学 | Polycarboxylic acid ester dispersing agent, synthesis method thereof and application of polycarboxylic acid ester dispersing agent in pesticide auxiliary agent |
| CN118005979A (en) * | 2023-04-03 | 2024-05-10 | 常州逸冠塑料制品有限公司 | Preparation method of high-strength wear-resistant engineering plastic |
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